SG191888A1 - Method of making diacetal compound in aqueous medium - Google Patents
Method of making diacetal compound in aqueous medium Download PDFInfo
- Publication number
- SG191888A1 SG191888A1 SG2013052444A SG2013052444A SG191888A1 SG 191888 A1 SG191888 A1 SG 191888A1 SG 2013052444 A SG2013052444 A SG 2013052444A SG 2013052444 A SG2013052444 A SG 2013052444A SG 191888 A1 SG191888 A1 SG 191888A1
- Authority
- SG
- Singapore
- Prior art keywords
- acid
- group
- reaction
- sorbitol
- naphthaldehyde
- Prior art date
Links
- -1 diacetal compound Chemical class 0.000 title claims abstract description 20
- 239000012736 aqueous medium Substances 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 4
- ZETHHMPKDUSZQQ-UHFFFAOYSA-N Betulafolienepentol Natural products C1C=C(C)CCC(C(C)CCC=C(C)C)C2C(OC)OC(OC)C2=C1 ZETHHMPKDUSZQQ-UHFFFAOYSA-N 0.000 title description 2
- HEOKFDGOFROELJ-UHFFFAOYSA-N diacetal Natural products COc1ccc(C=C/c2cc(O)cc(OC3OC(COC(=O)c4cc(O)c(O)c(O)c4)C(O)C(O)C3O)c2)cc1O HEOKFDGOFROELJ-UHFFFAOYSA-N 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000012530 fluid Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 19
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 19
- 239000000600 sorbitol Substances 0.000 claims abstract description 19
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 claims abstract description 15
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000005846 sugar alcohols Chemical class 0.000 claims abstract description 14
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 150000001299 aldehydes Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 17
- 235000002639 sodium chloride Nutrition 0.000 claims description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 13
- 235000019743 Choline chloride Nutrition 0.000 claims description 13
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 13
- 229960003178 choline chloride Drugs 0.000 claims description 13
- 239000000852 hydrogen donor Substances 0.000 claims description 13
- 150000008040 ionic compounds Chemical class 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 11
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052751 metal Chemical class 0.000 claims description 9
- 239000002184 metal Chemical class 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000012429 reaction media Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000001431 2-methylbenzaldehyde Substances 0.000 claims description 6
- WMPDAIZRQDCGFH-UHFFFAOYSA-N 3-methoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1 WMPDAIZRQDCGFH-UHFFFAOYSA-N 0.000 claims description 6
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 6
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 6
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims description 6
- POQJHLBMLVTHAU-UHFFFAOYSA-N 3,4-Dimethylbenzaldehyde Chemical compound CC1=CC=C(C=O)C=C1C POQJHLBMLVTHAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 3
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims description 3
- ZWUSBSHBFFPRNE-UHFFFAOYSA-N 3,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1Cl ZWUSBSHBFFPRNE-UHFFFAOYSA-N 0.000 claims description 3
- CASRSOJWLARCRX-UHFFFAOYSA-N 3,5-dichlorobenzaldehyde Chemical compound ClC1=CC(Cl)=CC(C=O)=C1 CASRSOJWLARCRX-UHFFFAOYSA-N 0.000 claims description 3
- ASOFZHSTJHGQDT-UHFFFAOYSA-N 3,5-difluorobenzaldehyde Chemical compound FC1=CC(F)=CC(C=O)=C1 ASOFZHSTJHGQDT-UHFFFAOYSA-N 0.000 claims description 3
- NBEFMISJJNGCIZ-UHFFFAOYSA-N 3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C)=CC(C=O)=C1 NBEFMISJJNGCIZ-UHFFFAOYSA-N 0.000 claims description 3
- TZUUPGZANQRCHD-UHFFFAOYSA-N 3-bromo-4-ethoxybenzaldehyde Chemical compound CCOC1=CC=C(C=O)C=C1Br TZUUPGZANQRCHD-UHFFFAOYSA-N 0.000 claims description 3
- FAHZIKXYYRGSHF-UHFFFAOYSA-N 3-bromo-4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1Br FAHZIKXYYRGSHF-UHFFFAOYSA-N 0.000 claims description 3
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 claims description 3
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 claims description 3
- QZMGMXBYJZVAJN-UHFFFAOYSA-N 3-ethoxybenzaldehyde Chemical compound CCOC1=CC=CC(C=O)=C1 QZMGMXBYJZVAJN-UHFFFAOYSA-N 0.000 claims description 3
- PIKNVEVCWAAOMJ-UHFFFAOYSA-N 3-fluorobenzaldehyde Chemical compound FC1=CC=CC(C=O)=C1 PIKNVEVCWAAOMJ-UHFFFAOYSA-N 0.000 claims description 3
- KDHUZENESNYYHR-UHFFFAOYSA-N 3-hex-1-ynylbenzaldehyde Chemical compound CCCCC#CC1=CC=CC(C=O)=C1 KDHUZENESNYYHR-UHFFFAOYSA-N 0.000 claims description 3
- LXPWGAZYJHUWPM-UHFFFAOYSA-N 4-(2-methylpropyl)benzaldehyde Chemical compound CC(C)CC1=CC=C(C=O)C=C1 LXPWGAZYJHUWPM-UHFFFAOYSA-N 0.000 claims description 3
- BEOBZEOPTQQELP-UHFFFAOYSA-N 4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C=C1 BEOBZEOPTQQELP-UHFFFAOYSA-N 0.000 claims description 3
- ARIREUPIXAKDAY-UHFFFAOYSA-N 4-butylbenzaldehyde Chemical compound CCCCC1=CC=C(C=O)C=C1 ARIREUPIXAKDAY-UHFFFAOYSA-N 0.000 claims description 3
- AZMDWRPTDCIFRD-UHFFFAOYSA-N 4-chloro-3-fluorobenzaldehyde Chemical compound FC1=CC(C=O)=CC=C1Cl AZMDWRPTDCIFRD-UHFFFAOYSA-N 0.000 claims description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims description 3
- JRHHJNMASOIRDS-UHFFFAOYSA-N 4-ethoxybenzaldehyde Chemical compound CCOC1=CC=C(C=O)C=C1 JRHHJNMASOIRDS-UHFFFAOYSA-N 0.000 claims description 3
- NNHYTIOMCJAWLM-UHFFFAOYSA-N 4-fluoro-3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C=O)=CC(C)=C1F NNHYTIOMCJAWLM-UHFFFAOYSA-N 0.000 claims description 3
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 claims description 3
- MYLBIQHZWFWSMH-UHFFFAOYSA-N 4-methoxy-3-methylbenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1C MYLBIQHZWFWSMH-UHFFFAOYSA-N 0.000 claims description 3
- TYNJQOJWNMZQFZ-UHFFFAOYSA-N 4-prop-2-enoxybenzaldehyde Chemical compound C=CCOC1=CC=C(C=O)C=C1 TYNJQOJWNMZQFZ-UHFFFAOYSA-N 0.000 claims description 3
- FGXZWMCBNMMYPL-UHFFFAOYSA-N 4-propoxybenzaldehyde Chemical compound CCCOC1=CC=C(C=O)C=C1 FGXZWMCBNMMYPL-UHFFFAOYSA-N 0.000 claims description 3
- MAUCRURSQMOFGV-UHFFFAOYSA-N 4-propylbenzaldehyde Chemical compound CCCC1=CC=C(C=O)C=C1 MAUCRURSQMOFGV-UHFFFAOYSA-N 0.000 claims description 3
- NYNSNUNMTUNAEO-UHFFFAOYSA-N 5,6,7,8-tetrahydronaphthalene-2-carbaldehyde Chemical compound C1CCCC2=CC(C=O)=CC=C21 NYNSNUNMTUNAEO-UHFFFAOYSA-N 0.000 claims description 3
- LROJZZICACKNJL-UHFFFAOYSA-N Duryl aldehyde Chemical compound CC1=CC(C)=C(C=O)C=C1C LROJZZICACKNJL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000003935 benzaldehydes Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010952 in-situ formation Methods 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 claims description 3
- 229940081310 piperonal Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GISVICWQYMUPJF-UHFFFAOYSA-N 2,4-Dimethylbenzaldehyde Chemical compound CC1=CC=C(C=O)C(C)=C1 GISVICWQYMUPJF-UHFFFAOYSA-N 0.000 claims description 2
- SSTRYEXQYQGGAS-UHFFFAOYSA-N 3,4-diethoxybenzaldehyde Chemical compound CCOC1=CC=C(C=O)C=C1OCC SSTRYEXQYQGGAS-UHFFFAOYSA-N 0.000 claims description 2
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims 1
- ZLDMZIXUGCGKMB-UHFFFAOYSA-N 3,5-dibromobenzaldehyde Chemical compound BrC1=CC(Br)=CC(C=O)=C1 ZLDMZIXUGCGKMB-UHFFFAOYSA-N 0.000 claims 1
- CHHSYJHKOZHOAY-UHFFFAOYSA-N 3-hydroxy-5-methyl-8-propan-2-ylnaphthalene-2-carbaldehyde Chemical compound OC1=C(C=O)C=C2C(C(C)C)=CC=C(C)C2=C1 CHHSYJHKOZHOAY-UHFFFAOYSA-N 0.000 claims 1
- 235000008979 vitamin B4 Nutrition 0.000 claims 1
- 239000011579 vitamin B4 Substances 0.000 claims 1
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000386 donor Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229960001231 choline Drugs 0.000 description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PFNMQJSEHLYYLS-UHFFFAOYSA-N 3-hydroxy-5,6,7,8-tetrahydronaphthalene-2-carbaldehyde Chemical compound C1CCCC2=C1C=C(O)C(C=O)=C2 PFNMQJSEHLYYLS-UHFFFAOYSA-N 0.000 description 2
- MGPYTUGHWZINMT-UHFFFAOYSA-N 3-methoxy-5,6,7,8-tetrahydronaphthalene-2-carbaldehyde Chemical compound C1CCCC2=C1C=C(OC)C(C=O)=C2 MGPYTUGHWZINMT-UHFFFAOYSA-N 0.000 description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
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- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical class C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- GEICDMWIZIQEEI-UHFFFAOYSA-N 2,3-dibromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1Br GEICDMWIZIQEEI-UHFFFAOYSA-N 0.000 description 1
- NTWBHJYRDKBGBR-UHFFFAOYSA-N 2-ethylbenzaldehyde Chemical compound CCC1=CC=CC=C1C=O NTWBHJYRDKBGBR-UHFFFAOYSA-N 0.000 description 1
- DTALCVXXATYTQJ-UHFFFAOYSA-N 2-propan-2-ylbenzaldehyde Chemical compound CC(C)C1=CC=CC=C1C=O DTALCVXXATYTQJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
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- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
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- 230000001256 tonic effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
This invention is directed to a process for preparation of acetal derivatives, 1,3:2,4-bis (3,4-dimethylbenzylidene) sorbitol (DMDBS) and 1,3:2,4-bis (4-methylbenzylidene) sorbitol (MDBS) by carrying out a dehydrocondensation reaction by betweeen an aldehyde and an alditol using an aqueous ionic fluid as the acid catalyst.
Description
METHOD OF MAKING DIACETAL COMPOUND IN AQUEOUS MEDIUM
This invention relates to a method of producing alditol acetals in an aqueous ionic fluid.
The acetal compound is the reaction product of an alditol and benzaldehyde. Alditol acetals, such as 1,3:2,4-bis (4-methylbenzylidene) sorbitol (MDBS) and 1,3:2,4-bis (3,4-dimethylbenzylidene) sorbitol (DMDBS) derivative compounds are known compounds which find their utility as an additive in polypropylene. Acetals of substituted and unsubstituted aldehydes are also known to be useful as nucleating agents, gelling agents, processing aids, and strength modifiers in polyolefin resins, polyester resins, deodorant, and antiperspirant compositions; hydrocarbon fuels and paints. Bn
Acetal alditols are typically prepared by the condensation reaction of an aromatic aldehyde with an alditol containing 6 carbon atoms like sorbitol. For MDBS and
DMDBS structures, such reactions involve two moles of the aldehyde and one mole of an alditol.
Several methods for the preparation of acetal alditols have been reported in US 4,267,110, US 3,721,682, US 4,429,140; US 4,562,265; US 4,902,807; US 5,023,354;
US 5,731,474 and US 6,500,964.
The hitherto reported methods suffer from several shortcomings. Majority of the earlier known processes employ various organic solvents which necessitates high temperature for carrying out the reaction thereby increasing the cost component. Furthermore, most of solvents are very expensive and they too render the process un-economical.
Attempts have been made in the past to overcome the above mentioned shortcomings by - employing the acidic catalyst for improving the yield and the versatility (ability to employs variety of substituted aldehydes) the process.
The presently known processes for the preparation of acetals which employ acidic catalysts still suffer from several limitations. Though mineral acids serve as good catalysts for the acetalization process, they are very corrosive in nature. Furthermore, the final product resulting from such processes needs to be purified by neutralizing the residual free acid. Though the yields offered by all teachings are acceptable for the practical purposes, all the methods are not effective from the perspective of versatility, environmentally friendliness, energy efficient, reliability, cost-effective, and safe production.
Ionic systems, which are examples of viscous molten salts, have a number of interesting and useful properties, and have utility, for example, as highly polar solvents, and catalyst in synthetic chemistry. They also have been found to be useful in applications in various fields such as electrochemistry, synthesis of chemical compounds, dyes, batteries, fuel cells, photovoltaic devices, electro-deposition processes, semi conductor cleaning, pyrolysis, gasification, in applications involving cellulose dissolution, for the electroplating of metals as described, for example in US Patent No. 6573405, US Patent
No. 7183433, US Patent No. 7196221, US Patent Appl. No. 2005/0147889, US Patent
No. 6527977, US Patent Appl. No.2008/0307703, US Patent Appl. No. 2006/0183654,
US Patent Appl. No. 2009/0247432.
Tonic compounds / liquids prepared from quaternary ammonium salt as one of the ions have been reported in US 5,892,124, US 5104840, US 6573405, US 7183433 and US 7196221. Ionic compounds / liquids made from choline chloride and metal salts in particular are also known.
Ionic liquids exhibit very low or no vapour pressure and thus, in contrast to many conventional molecular solvents produce virtually no vapours. They are therefore advantageous from a health, safety and environmental point of view.
Processes for preparation of acetals and di-acetals other than MDBS and DMDBS structures using ionic liquids as catalysts and/or reaction medium have been reported.
For example, CN 101440025 discloses a method for preparation of ethylidene ether or ketal which employs N-methyl glyoxaline bisulphate ionic liquid catalyst. Other patents - which disclose the use of ionic liquids as catalyst for preparation of acetals other than
MDBS and DMDBS structures include CN 101723852, CN 101544628 and CN 1858048.
None of the hitherto reported processes for preparation of MDBS and DMDBS have employed ionic compounds / liquids as catalysts and/or reaction medium. There exists a need for process for preparation of MDBS and DMDBS which uses ionic compounds / liquids as the catalyst and or reaction medium. There also remains a need for a process for preparation of acetals, particularly MDBS and DMDBS which does not employ any expensive solvents and cqrrosive mineral acids.
As used in the present specification, the following words and phrases are generally intended to have the meanings as set forth below, except to the extent that the context in which they are used indicates otherwise.
The phrase “aqueous ionic fluid” is used herein to refer to the solvate prepared whereby ionic compound is formed in-situ by dissolving the mixture of a hydrogen donor ~ selected from the group consisting of methanesulfonic acid (MSA), para toluenesulfonic acid (PTSA), oxalic acid, citric acid, benzoic acid, maleic acid and tartaric acid and a ‘counter ion providing compound’ selected from the group consisting of a quaternary ammonium salt, such as choline chloride and a metal salt such as sodium chloride and zinc chloride.
It is an object of the present invention to provide a process for preparation of alditol acetal derivative compounds in high yields and purity.
It is another object of the present invention to provide a process that allows the preparation of symmetrical and asymmetrical dibenzylidene sorbitol compounds without any limitation.
It is still another object of the present invention to provide a process for preparation of acetal derivatives which is economical.
It is yet another object of the present invention to provide a process for preparation of acetal derivatives which is environment friendly.
It is yet another object of the present invention to provide a process for preparation of acetal derivatives wherein there the final product is devoid of any residual free acid.
It is yet another object of the present invention to provide a process for preparation of acetal derivatives which is safe.
It is a further object of the invention to provide a method which allows the production of monoacetal and diacetal derivatives without the formation of triacetal derivates.
In accordance with the present invention there is provided a process for preparation of acetal derivatives selected from the group consisting of 1,3:2,4-bis (4-
methylbenzylidene) sorbitol (MDBS), 1,3:2,4-bis (3,4-dimethylbenzylidene) sorbitol (DMDBS) comprising the following steps: - preparing an aqueous ionic fluid; : - carrying out dehydrocondensation reaction by adding an aldehyde and an alditol in a mole ratio of 2:1 in the ionic fluid under continuous stirring to form a reaction mixture; - stirring the resultant reaction mixture to maintain the contents in a suspension form; and : - discontinuing the stirring of the reaction mixture to allow the mass formed in the reaction mixture to settle; - isolating and purifying the mass by filtering, washing and drying to obtain an acetal derivative without any free acid residue present therein.
Typically, the aqueous ionic fluid acts as a catalyst for the dehydrocondensation reaction.
Additionally, the ‘aqueous jonic fluid acts as a reaction medium for the dehydrocondensation reaction.
Typically, the aqueous ionic fluid comprises an ionic compound formed by the hydrogen bonding between a hydrogen donor selected from the group consisting of methanesulfonic acid (MSA), para toluenesulfonic acid (PTSA), oxalic acid, citric acid, benzoic acid, maleic acid and tartaric acid and a counterion from at least one counter-ion providing compound selected from the group consisting of choline chloride, sodium chloride and zinc chloride.
Typically, the aldehyde is at least one aldehyde selected from the group consisting of unsubstituted benzaldehyde, and substituted aldehydes including benzaldehyde, 4- methylbenzaldehyde, 3-methylbenzaldehyde, 4-propylbenzaldehyde, p-
ethylbenzaldehyde , 4-butylbenzaldehyde, 4-1sopropylbenzaldehyde, 4- isobutylbenzaldehyde, 2,4-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5- dimethylbenzaldehyde, 3-methyl-4-methoxybenzaldehyde, 2,4,5- trimethylbenzaldehyde, 3-hex-1-ynylbenzaldehyde, piperonal, 3-hydroxy-5,6,7,8- tetrahydro-2-naphthaldehyde, 3 -Methoxy-5,6,7,8-tetrahydro-2-naphthaldehyde, 3-
Hydroxy-8-isopropyl-5-methyl-2-naphthaldehyde, 2-naphthaldehyde, 3- methoxybenzaldehyde, 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3- ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 3,4-diethoxybenzaldehyde, 4- allyloxybenzaldehyde, 4 — propoxybenzaldehyde, 4-carboxybenzaldehyde, 3- bromobenzaidehyde, 4-bromobenzaldehyde, 2-chlorobenzaldehyde, 3- chlorobenzaldehyde, 4-chlorobenzaldehyde, 3-fluorobenzaldehyde, 4- fluorobenzaldehyde, 3,4-dichlorobenzaldehyde, ~ 3,5-dichlorobenzaldehyde, 3.5- dibromobenzaldehyde, 3,5-difluorobenzaldehyde, 4-chloro-3-fluorobenzaldehyde, 3- bromo-4-fluorobenzaldehyde , 4-fluoro-3-methyl-, 5,6,7,8-tetrahydro-2- naphthaldehyde, 4-fluoro-3,5-dimethylbenzaldehyde, 4-(trifluoromethyl)benzaldehyde, 3-bromo-4-ethoxybenzaldehyde and mixtures thereof.
Typically, the alditol is selected from the group consisting of sorbitol (100%), and iso- propyl sorbitol. Preferably, alditol is an aqueous solution of sorbitol with a concentration in the range of about 40 % to about 99%.
Typically, the method step of stirring is carried out for a period in the range of about 6 to 10 hours. | :
In accordance with one embodiment, the process of the present invention further comprises a method step of adding a surface active agent during the dehydrocondensation reaction; said surface active agent being selected from the group consisting of anionic surface active agent, cationic surface agent and nonionic surface active agent. In accordance with one embodiment, choline chloride, a cationic surface active agent is employed during the dehydrocondensation reaction. :
Typically, the method step of preparing an aqueous ionic fluid comprises adding a hydrogen donor and a ‘counter ion providing compound’ independently in equimolar quantities to water leading to the in-situ formation of an ionic compound in water.
Typically, the hydrogen donor is selected from the group consisting of at least one acid selected from the group consisting of methanesulfonic acid (MSA), para toluenesulfonic acid (PTSA), oxalic acid, citric acid, benzoic acid, maleic acid and tartaric acid.
Typically, the counter ion providing compound is at least one selected from the group consisting of a quaternary ammonium salt and a metal salt. oo ‘Typically, the quaternary ammonium salt is choline chloride and the metal salt is at least one selected from the group consisting of zinc chloride and sodium chloride.
In order to overcome the shortcomings of the hitherto reported processes which employ expensive solvents and corrosive mineral acid catalysts for the preparation of acetals, the inventors of the present invention have chosen the specific ionic fluids for the preparation of the acetals, particularly DMDBS and MDBS.
Accordingly, in a first aspect of the present invention there is provided a process for preparation of acetal derivatives particularly, DMDBS and MDBS by dehydrocondensation reaction between an aldehyde and alditol using an aqueous ionic fluid which serves the dual role of a reaction catalyst and a reaction medium, comprising the following steps: : - preparing an aqueous ionic fluid,
- carrying out the dehydrocondensation reaction by adding an aldehyde and an alditol - in a mole ratio of 2:1 in the ionic fluid under continuous stirring to form a reaction mixture; - stirring the resultant reaction mixture to maintain the contents in a suspension form; and - discontinuing the stirring of the reaction mixture to allow the mass formed in the reaction mixture to settle; : '- isolating and purifying the mass by filtering, washing and drying to obtain an acetal derivative without any free acid residue present therein.
The aqueous ionic fluid comprises an ionic compound formed from the hydrogen bonding between a hydrogen donor and a counter ion which catalyses the dehydrocondensation. Besides, it also serves as a reaction medium for carrying out the reaction. Typically, the method step of preparing an ionic fluid comprises adding a - hydrogen donor and a counter ion providing compound independently in equimolar quantities to water leading to the in-situ formation of an ionic compound in water.
Typically, the hydrogen donor is selected from the group consisting of at least one acid - selected from the group consisting of methanesulfonic acid (MSA), para toluenesulfonic acid (PTSA), oxalic acid, citric acid, benzoic acid, maleic acid and tartaric acid.
Typically, the counter ion providing compound is at least one selected from the group consisting of a quaternary ammonium salt and a metal salt. Typically, the quaternary ammonium salt is choline chloride. Typically, the metal salt is at least one selected from the group consisting of zinc chloride and sodium chloride. :
The counter ion providing compounds provide counter ion that are capable of forming a hydrogen bond in aqueous medium or aqueous-solvent mixture. The ionic compound formation by result of cations and anions connection by hydrogen bond were reported to .
have supramolecular structural organization (Olivier-Bourbigou, H., et al., Applied
Catalysis A: General, 373, 1-56, 2010; Deetlefs, M., et al., J. Physical Chemistry B. 110, 12055-12061, 2006; Canongia Lopez, J. N. and Padua, A. A. H., J. Physical
Chemistry B. 110, 3330-3335, 2006). The continuous microdomains structure formed due to the network of hydrogen bond seem to be favorable for catalytic reactions since acid is not available in free form and this will not impart any residual acidity to the final . product. ~The aldehyde employed in the process of the present invention is at least one selected from the group consisting of unsubstituted benzaldehyde, and substituted aldehydes including benzaldehyde, 4-methylbenzaldehyde, 3-methylbenzaldehyde, 4- propylbenzaldehyde, p-ethylbenzaldehyde , 4-butylbenzaldehyde, 4-
Isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 2.,4-dimethylbenzaldehyde, 3,4- dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 3-methyl-4-methoxybenzaldehyde, 2,4,5-trimethylbenzaldehyde, 3-hex-1-ynylbenzaldehyde, piperonal, 3-hydroxy-5,6,7,8- tetrahydro-2-naphthaldehyde, 3 -Methoxy-5,6,7,8-tetrahydro-2-naphthaldehyde, 3-
Hydroxy-8-isopropyl-5-methyl-2-naphthaldehyde, 2-naphthaldehyde, . 3- methoxybenzaldehyde, 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3- ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 3.,4-diethoxybenzaldehyde, 4- allyloxybenzaldehyde, 4 — propoxybenzaldehyde, 4-carboxybenzaldehyde, 3- bromobenzaldehyde, 4-bromobenzaldehyde, 2-chlorobenzaldehyde, 3- chlorobenzaldehyde, 4-chlorobenzaldehyde, 3-fluorobenzaldehyde, 4- fluorobenzaldehyde, 3,4-dichlorobenzaldehyde, 3,5-dichlorobenzaldehyde, 3,5- ~ dibromobenzaldehyde, 3,5-difluorobenzaldehyde, 4-chloro-3-fluorobenzaldehyde, 3- bromo-4-fluorobenzaldehyde , 4-fluoro-3-methyl-, 5,6,7,8-tetrahydro-2- naphthaldehyde, 4-fluoro-3,5-dimethylbenzaldehyde, 4-(trifluoromethyl)benzaldehyde, 3-bromo-4-ethoxybenzaldehyde and mixtures thereof.
Typically, the alditol used in accordance with the process of the present invention is selected from the group consisting of sorbitol (100%), and iso-propyl sorbitol.
Alternatively, an aqueous solution of sorbitol with a concentration in the range of about 40 % to about 99% is used as the alditol.
One notable problem that is frequently encountered in the preparation of the acetals is solubility of the aldehyde component in water. According to the present invention, a quaternary ammonium salt which is capable of forming an ionic compound also serves as cationic surfactant/emulsifier to improve the solubility of reactant (aldehyde) in aqueous medium. Optionally, a surface active agent is added to the reaction mixture during the dehydrocondensation reaction. Typically, choline chloride is used as the surface active agent. Typically, the dehydrocondensation reaction is carried out at a temperature with a range of about 25 °C to about 50 °C.
Typically, the method step of stirring is carried out for a period in the range of about 6 to 10 hours.
The inventors of the present invention have surprisingly found out that the product obtained by the process of the present invention was completely free of any residual free acid. The residual free acid in the product is highly undesirable since it promotes the hydrolysis of the end product at high temperature, especially during the drying process.
The process of the present invention is therefore particularly advantageous since it obviates the need for neutralizing residual free acid in the end product thereby reducing the cost and complexity of the process. This demonstrates the utility of the ionic fluids as a catalyst and reaction medium to carry out the acid based dehydrocondensation reactions.
The following examples further illustrate the present invention but are not to be construed as limiting the invention as defined in the claims appended hereto.
Example: 1
Toluene-4-sulphonic acid monohydrate (PTSA), a hydrogen donor (1.9 gms) was mixed with choline chloride (1.4 gms) in equal mole ratio and water was added to the salt mixture and stirred well to prepare ionic fluid. 3,4 dimethyl benzaldehyde and sorbitol in 2:1 mole ratio were added to the ionic compound and stirred to initiate the reaction. The solid mass formed within few minutes of starting the reaction. The stirring speed was increased to keep the mass in suspension condition and reaction was continued for 8 hrs. The solid product was filtered and "washed with 100 ml methanol. The white solid product was dried in oven at 95°C for 2 hrs followed by air dried for 4 hrs for measuring the yield. The yield was found to be 60%.
Example: 2 - 6 . The procedure of example 1 was followed for different hydrogen donor compounds as given in Table 1 with choline chloride.
Example: 7-18
The procedure of example 1 is followed for different hydrogen donors as given in Table 2 and Table 3 with zinc chloride and sodium chloride respectively.
Example: 19 - 21
The procedure of example 1 was followed except, additional 0.01 moles of choline chloride was added to the water. The yield was found to be 69%. Similarly for PTSA — sodium and zinc chloride systems, the addition of 0.01 moles of choline chloride improved the yields.
Table 1: Details of the reactions carried for examples 1- 5 for the procedure described in the example : Table 1
Example | Ratio of | Water, | Choline | Hydrogen Reaction | Yield,
No Sorbitol | ml chloride, | Donor, Time, % to gm (gm) Hrs
Aldehyde
AOA [6 [5 [3 1:2 2.8 Oxalic Acid 50 1.3 4 1:2 4.2 Citric Acid 10 20 2.1 [5 1:2 30 Benzoic ~~ [10 33
Acid(1.22 1:2 30 Maleic Acid | 10 35 : : 1.16 ‘Table 2: Details of the reactions carried out for examples 7-12 with the procedure described in the example 1
Example Ratio of | Water, Zinc Hydrogen Reaction | Yield,
No Sorbitol to mi chloride, | Donor, Time, % : Aldehyde gm (gm) Hrs 8 J1:2 Jo 10.68 [MSA(0.96) [6 [21
Ps [ei Jae Je 1.3 a : 2.1 11 1:2 30 1.36 | Benzoic 10 25
Acid(2.44 1.16
Table 3: Details of the reactions carried out for examples 13-18 with the procedure described in the example 1
Example | Ratio of | Water, | Sodium | Hydrogen Reaction | Yield, ~ | No | Sorbitol | mi chloride, | Donor, Time, % to gm (gm) Hrs
Aldehyde
MAGS [6 |W 1:2 130 1.16 Oxalic Acid 35 i (1.3) 116 1:2 30 1.74 Citric Acid | 15 (2.1) 17 1:2 . 30 0.58 Benzoic 10 10
Acid(1.22) 18 1:2 30 0.58 Maleic Acid 30 (1.16)
Table 4: Details of the reactions carried out for examples 19-21 with the procedure described in the example 1
Example | Ratio of | Water, | Choline | Hydrogen | Reaction | Yield,
No Sorbitol | ml chloride, | Donor, Time, % to gm (gm) Hrs
Aldehyde 1 19 1:2 30 Choline | PTSA (1.9) = chloride : (1.4) 1:2 NaCl PTSA (1.9) 65 (0.58) 21 1:2 ZnCl, PTSA (3.8) (1.36)
While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Variations or modifications to the design and construction of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the invention. :
The numerical values given for various physical parameters, dimensions and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the invention and the claims unless there is a statement in the specification to the contrary.
Claims (13)
1. A process for preparation of acetal derivatives selected from the group consisting of 1,3:2,4-bis (3,4-dimethylbenzylidene) sorbitol (DMDBS) and 1,3:2,4-bis (4- methylbenzylidene) sorbitol (MDBS) comprising the following steps: - preparing an aqueous ionic fluid; - carrying out a dehydrocondensation reaction by adding an aldehyde and an alditol in a mole ratio of 2:1 in the ionic fluid under continuous stirring’ to form a reaction mixture; - stirring the resultant reaction mixture to maintain the contents in a suspension form; and - discontinuing the stirring of the reaction mixture to allow the mass formed in the reaction mixture to settle; - isolating and purifying the mass by filtering, washing and drying to obtain an acetal derivative without any free acid residue present therein.
2. A process as claimed in claim 1, wherein the aqueous ionic fluid acts as a catalyst for the dehydrocondensation reaction.
3. A process as claimed in claiml, wherein the aqueous ionic fluid acts as a reaction medium for the dehydrocondensation reaction. :
4. A process as claimed in claiml, wherein the aqueous ionic fluid comprises an ionic compound formed by the hydrogen bonding between at least one hydrogen donor selected from the group consisting of methanesulfonic acid (MSA), para toluenesulfonic acid (PTSA), oxalic acid, citric acid, benzoic acid, maleic acid and tartaric acid and at least one counter ion from at least one counter ion providing compound selected from the group consisting of cholin chloride, sodium chloride and zinc chloride. :
5. A process as claimed in claiml, wherein the aldehyde is at least one aldehyde selected from the group consisting of unsubstituted benzaldehyde, and substituted aldehydes including benzaldehyde, 4-methylbenzaldehyde, 3- methylbenzaldehyde, 4-propylbenzaldehyde, p-ethylbenzaldehyde , 4- butylbenzaldehyde, 4-lsopropylbenzaldehyde, 4-isobutylbenzaldehyde, 2,4- dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 3-methyl-4-methoxybenzaldehyde, 2,4,5-trimethylbenzaldehyde, 3-hex-1- ynylbenzaldehyde, piperonal, 3-hydroxy-5,6,7,8-tetrahydro-2-naphthaldehyde, 3 } -Methoxy-5,6,7,8-tetrahydro-2-naphthaldehyde, 3-Hydroxy-8-isopropyl-5- methyl-2-naphthaldehyde, 2-naphthaldehyde, 3-methoxybenzaldehyde, 4- - methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4- ethoxybenzaldehyde, 3,4-diethoxybenzaldehyde, 4-allyloxybenzaldehyde, 4 — Propoxybenzaldehyde, 4-carboxybenzaldehyde, 3-bromobenzaldehyde, 4- ~ bromobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4- chlorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 3,4- dichlorobenzaldehyde, 3,5-dichlorobenzaldehyde, 3,5-dibromobenzaldehyde, 3,5-difluorobenzaldehyde, 4-chloro-3-fluorobenzaldehyde, 3-bromo-4- fluorobenzaldehyde , 4-fluoro-3-methyl-, 5,6,7,8-tetrahydro-2-naphthaldehyde, 4-fluoro-3,5-dimethylbenzaldehyde, 4-(trifluoromethyl)benzaldehyde, 3-bromo- 4-ethoxybenzaldehyde and mixtures thereof.
6. A process as claimed in claim 1, wherein the alditol is selected from the group consisting of sorbitol (100%), and iso-propyl sorbitol.
7. A process as claimed in claim 1, wherein the alditol is an aqueous solution of sorbitol with a concentration in the range of about 40 % to about 99%.
8. A process as claimed in claim 1, wherein the method step of stirring is carried out for a period in the range of about 6 to 10 hours. | :
9. A process as claimed in claim 1, further comprising the method step of adding a surface active agent during the dehydrocondesation reaction; wherein the surface active agent is choline chloride.
10. A process as claimed in claiml, wherein the method step of preparing an aqueous ionic fluid comprises adding a hydrogen donor and a ‘counter ion providing : compound’ independently in equimolar quantities to water leading to the in-situ formation of an ionic compound in water.
11. A process as claimed in claim 9, where in the hydrogen donor is selected from the group consisting of at least one acid selected from the group consisting of methanesulfonic acid (MSA), para toluenesulfonic acid (PTSA), oxalic acid, citric acid, benzoic acid, maleic acid and tartaric acid.
12. A process as claimed in claim 9, wherein the counter ion providing compound is at least one selected from the group consisting of a quaternary ammonium salt and a metal salt.
13. A process as claimed in claim 11, wherein the quaternary ammonium salt is choline chloride and the metal salt is at least one selected from the group consisting of zinc chloride and sodium chloride.
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Family Cites Families (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4843748B1 (en) | 1969-10-06 | 1973-12-20 | New Japan Chem Co Ltd | |
US4267110A (en) | 1978-11-29 | 1981-05-12 | E.C. Chemical Ind. Co., Ltd. | Process for preparing dibenzylidenesorbitol and composition containing the same |
US4562265A (en) | 1979-10-11 | 1985-12-31 | Milliken Research Corporation | Method for producing a di-acetal of sorbitol and an aromatic aldehyde |
US4429140A (en) * | 1981-12-29 | 1984-01-31 | New Japan Chemical Co., Ltd. | Process for preparing dibenzylidene sorbitols and dibenzylidene xylitols |
FR2613713B1 (en) | 1987-04-07 | 1989-08-04 | Roquette Freres | PROCESS FOR THE PREPARATION OF ALDITOL DIACETALS, IN PARTICULAR DIBENZYLIDENE-SORBITOL, IN AQUEOUS MEDIA |
JPH07107067B2 (en) | 1987-12-07 | 1995-11-15 | 新日本理化株式会社 | Method for producing acetals |
FR2659871B1 (en) | 1990-03-20 | 1992-06-05 | Inst Francais Du Petrole | NONAQUEOUS LIQUID COMPOSITION WITH IONIC CHARACTER AND USE THEREOF AS SOLVENT. INVENTION OF MM. YVES CHAUVIN, DOMINIQUE COMMEREUC, ISABELLE GUIBARD, ANDRE HIRSCHAUER, HELENE OLIVIER, LUCIEN SAUSSINE. |
FR2757850B1 (en) * | 1996-12-27 | 1999-04-16 | Inst Francais Du Petrole | IMPROVED PROCESS FOR DIENIC CONDENSATION CALLED DIELS-ALDER REACTION |
US5731474A (en) | 1997-01-31 | 1998-03-24 | Milliken Research Corporation | Method of making acetals |
JPH1121258A (en) * | 1997-07-02 | 1999-01-26 | Kuraray Co Ltd | Production of acetals |
US6214499B1 (en) | 1998-09-11 | 2001-04-10 | Eastman Kodak Company | Liquid crystalline filter dyes for imaging elements |
AU1672100A (en) | 1999-01-15 | 2000-08-01 | Bp Chemicals Limited | Ionic liquid catalyst for alkylation |
JP2000212115A (en) * | 1999-01-26 | 2000-08-02 | Nippon Shokubai Co Ltd | Production of acetal |
GB9906829D0 (en) | 1999-03-24 | 1999-05-19 | Univ Leicester | Ionic liquids |
GB0023708D0 (en) | 2000-09-27 | 2000-11-08 | Scionix Ltd | Hydrated salt mixtures |
GB0023706D0 (en) | 2000-09-27 | 2000-11-08 | Scionix Ltd | Ionic liquids |
US6500964B2 (en) * | 2001-03-23 | 2002-12-31 | Milliken & Company | Method of producing high yield alditol acetals with mineral acids and surfactants |
JP4554911B2 (en) | 2003-11-07 | 2010-09-29 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
WO2006007703A1 (en) | 2004-07-16 | 2006-01-26 | Simon Fraser University | Phosphonium ionic liquids as recyclable solvents for solution phase chemistry |
US20060079720A1 (en) | 2004-10-13 | 2006-04-13 | Milliken & Company | Method for preparing acetal-containing compositions |
US20060183654A1 (en) | 2005-02-14 | 2006-08-17 | Small Robert J | Semiconductor cleaning using ionic liquids |
WO2006117872A1 (en) | 2005-04-28 | 2006-11-09 | Kanto Denka Kogyo Co., Ltd. | Ionic fluid containing phosphonium cation and process for producing the same |
CN1903857B (en) * | 2005-07-29 | 2010-05-05 | 中国石油天然气集团公司 | Method of synthesizing high purity 1,3:2,4-di (3,4-dimethyl) benzyl cross sorbic alcohol |
JP2008285414A (en) | 2005-08-23 | 2008-11-27 | Katayama Seiyakushiyo:Kk | Phosphonium-type ionic liquid containing amino acid as constituent ion |
CN1858048A (en) | 2006-06-02 | 2006-11-08 | 浙江大学 | Method for preparing ketal in ionic liquid |
JP2008222592A (en) | 2007-03-09 | 2008-09-25 | Nippon Chem Ind Co Ltd | New phosphonium salt ionic liquid and reaction solvent using the same |
US7875090B2 (en) | 2007-04-24 | 2011-01-25 | The United States Of America As Represented By The Secretary Of Agriculture | Method and apparatus to protect synthesis gas via flash pyrolysis and gasification in a molten liquid |
JP5201620B2 (en) | 2007-08-30 | 2013-06-05 | 国立大学法人鳥取大学 | Phosphonium ionic liquid, method for producing biaryl compound and method for using ionic liquid |
CN101544628A (en) | 2008-03-24 | 2009-09-30 | 中国科学院兰州化学物理研究所 | Method for preparing acetal compound by room-temperature ionic liquid catalyst |
US8022014B2 (en) | 2008-03-26 | 2011-09-20 | Shrieve Chemical Products, Inc. | Deep eutectic solvents and applications |
CN101429083B (en) * | 2008-09-08 | 2010-12-15 | 华东师范大学 | Method for quick synthesis of alpha-single chloro-ketone compounds |
CN101723852B (en) | 2008-10-20 | 2012-10-17 | 浙江医药股份有限公司新昌制药厂 | Novel method for condensing aromatic aldehydes and active methylene compounds through catalysis of functional ionic liquid |
CN101440025B (en) | 2008-12-26 | 2012-07-11 | 安徽工业大学 | Method for preparing ethylidene ether or ketal by N-methyl glyoxaline bisulphate ion liquid catalysis |
WO2011026107A1 (en) | 2009-08-31 | 2011-03-03 | University Of Notre Dame Du Lac | Phthalanilate compounds and methods of use |
CN101665394B (en) * | 2009-09-22 | 2013-04-10 | 华东师范大学 | Method for directly preparing alpha-fluoro acetophenone by acetophenone one-pot method |
US9079156B2 (en) * | 2010-06-29 | 2015-07-14 | Reliance Industries Ltd. | Ionic fluids |
CN103402960B (en) | 2011-01-10 | 2015-06-10 | 瑞来斯实业有限公司 | Process for the preparation of alditol acetals |
-
2011
- 2011-02-28 CN CN201180066826.2A patent/CN103402959B/en not_active Expired - Fee Related
- 2011-02-28 US US13/978,579 patent/US8969595B2/en not_active Expired - Fee Related
- 2011-02-28 EP EP11855425.2A patent/EP2663541B1/en not_active Not-in-force
- 2011-02-28 JP JP2013548935A patent/JP5828005B2/en not_active Expired - Fee Related
- 2011-02-28 WO PCT/IN2011/000122 patent/WO2012095857A1/en active Application Filing
- 2011-02-28 KR KR1020137021042A patent/KR20140017548A/en not_active Application Discontinuation
- 2011-02-28 SG SG2013052444A patent/SG191888A1/en unknown
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WO2012095857A1 (en) | 2012-07-19 |
EP2663541A4 (en) | 2014-06-25 |
EP2663541B1 (en) | 2016-07-06 |
CN103402959B (en) | 2016-05-18 |
JP2014510034A (en) | 2014-04-24 |
US20130281716A1 (en) | 2013-10-24 |
JP5828005B2 (en) | 2015-12-02 |
KR20140017548A (en) | 2014-02-11 |
CN103402959A (en) | 2013-11-20 |
EP2663541A1 (en) | 2013-11-20 |
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